Process for treating the product mixture from the epoxidation of olefinic hydrocarbons

ABSTRACT

This invention relates to a process for reducing the acidic catalyst characteristics of an epoxidation reaction mixture resulting from the catalytic epoxidation of an olefin with an organic hydroperoxide.

United States Patent Kollar Jan. 14, 1975 PROCESS FOR TREATING THEPRODUCT [56] References Cited MIXTURE FROM THE EPOXIDATION OF UNITEDSTATES PATENTS OLEFINIC HYDROCARBONS 3,013,024 12/1961 Payne 26()/348.5[75] Inventor: John Kollar, Wallington, N..l. 3,062,841 11/1962 Yang etal. 26()/348.5

{73] Assignee: Halcon International, Inc., New OTHER PUBLICATIONS YorkHawkins, J, Chem. Soc," 1950, pp. 2169-2173. 22] Filed: Nov. 7, 1969Morrison et al., Organic Chemistry." 1959, pp. [21] Appl' 871522 114115. and 335-339, QD251.M72.

Related US. Application Data [63] Continuation of Ser. No. 684,563, Nov.20, 1967, Primary Examiner-Bernard Helfin abandoned, which is acontinuation of Ser. No. Assistant E i N m- P Morgenstem 9 3 2 %g%Attorney, Agent, or Firm-William c. Long; David COI'I mua lOII-ln'PaI' 0er. 0. Lll'lC 1964 abandone Dick, R1ggs T. Stewart [52 US. Cl.260/6I8 c,260/348.5 L, 260/348.5 v, ABSTRACT 260/617 260/586 R, 260/594, 260/631This invention relates to a process for reducing the 260/632 C acidiccatalyst characteristics of an epoxidation reac- Cl. {ion mixtureresulting from the atalytic epoxidation [58] Field of Search... 260/618C, 348.5 LL, 617 H, f an l fi with an Organic (impel-(mu 260/617 M, 631R, 632 C, 632 R 12 Claims, N0 Drawings PROCESS FOR TREATING THE PRODUCTMIXTURE FROM THE EPOXIDATION OF OLEFINIC HYDROCARBONS This applicationis a continuation of Application Ser. No. 684,563, filed Nov. 20, 1967which is a continuation of application Ser. No. 409,941, filed Nov. 9,1967 which is a continuation-in-part of application Ser. No. 375,313,filed June 15, 1964 all now abandoned.

The present invention is concerned with the treatment of reactionmixtures which result from the metal catalyzed epoxidation ofolefinically unsaturated compounds to the corresponding oxirane compoundusing organic hydroperoxides.

Important advances have been made in the production of oxirane compoundsthrough the reaction of olefinic materials with organic hydroperoxides.In these processes, certain difficulties are encountered in thesuccessful separation of products and by-products from the reactionmixtures. Specifically, the organic alcohol by-product which is formedby reduction of the organic hydroperoxide tends to undergo considerabledehydration during the subsequent recoveryprocedures. The alcoholdehydrates to the corresponding olefin which latter product undergoesvery rapid polymerization to highboiling residues. These residueseventually have to be removed as a useless product of the reaction. Inaddition, water, of course, if formed which complicates recoveryprocedures.

It is an object of the present invention to provide a method for thetreatment of reaction mixtures resulting from the epoxidation of olefinswith an organic hydroperoxide.

It is a particular object to provide a method whereby dehydration ofby-product alcohol is suppressed during the effluent work-up procedures.

Other objects will be apparent from the following description of theinvention.

It has been discovered that the epoxidation effluent mixtures whichresult from olefin epoxidations using a metal catalyst and an organichydroperoxide reactant are strongly acidic in nature. As a result ofthis strongly acidic nature, during subsequent distillations dehydrationof by-product alcohol occurs at the distillation temperatures. Now, inaccordance with the present invention, the epoxidation reaction effluentis treated prior to the distillation in order to reduce the acidcharacteristics thereof.

In one embodiment, there is incorporated with the reaction mixture abasic material such as sodium hydroxide in an amount sufficient toreduce the acidic characteristics of the effluent to the point wherelittle or no alcohol dehydration takes place during subsequentdistillation.

In another embodiment of the invention, the epoxidation effluent istreated with a chemical reducing agent whereby a similar effectivereduction in acidity is achieved.

In still another embodiment, the effluent is subjected to hydrogenationusing hydrogen and an appropriate catalyst to achieve the same acidityreduction.

Through practice of the present invention, the epoxidation effluentmixture can conveniently be treated as by distillation for theseparation and recovery of various constituents without encountering thedisadvantages of alcohol dehydration, the formation of highboilingresidues, and the loss of valuable products in the effluent.

The epoxidations are carried out in accordance with various techniqueswhich are the subject of earlier pa? tent applications. Olefins whichare epoxidized to the corresponding oxirane compounds includesubstituted and unsubstituted aliphatic and alicyclic olefins which maybe hydrocarbon, esters, alcohols, ketones, ethers, or the like.Preferred compounds are those having from about two to 30 carbon atoms,and preferably at least threejcarbon atoms. Illustrative olefins areethylene, propylene, normal butylene, isobutylene, the pentenes, themethyl pentenes, the normal hexenes, the octenes, the dodecenes,cyclohexene, methyl cyclohexene, butadiene, styrene, methyl styrene,vinyl toluene, vinylcyclohexene, the phenyl cyclohexenes, and the like.Olefins having halogen, oxygen, sulfur and the like containingsubstituents can be used. Such substituted olefins are illustrated byallyl alcohol, methallyl alcohol, cyclohexanol, diallyl ether, methylmethacrylate, methyl oleate, methyl vinyl ketone, allyl chloride, andthe like. In general, all olefinic materials epoxidized by methodspreviously employed can be epoxidized in accordance with this processincluding olefinically unsaturated polymers.

The lower olefins having about three or four carbon atoms in analiphatic chain are especially advantageously epoxidized by thisprocess.

The hydroperoxides which are employed in the invention are those havingthe formula ROOI-I wherein R is a substituted or unsubstituted alkyl,cycloalkyl or aralkyl radical having about three to 20 carbon atoms. Rmay be a heterocyclic or like radical.

Illustrative and preferred hydroperoxides are cumene hydroperoxide,ethylbenzene hydroperoxide, tertiary butyl hydroperoxide, cyclohexanoneperoxide, tetralin hydroperoxide, methyl ethyl ketone peroxide,methylcyclohexane hydroperoxide, and the like. The aralkylhydroperoxides are especially useful.

The epoxidation catalyst includes compounds of the following: Ti, V, Cr,Se, Zr, Nb, Mo, Te, Ta, W, Re, U. These may be characterized as formingperacids or as hydroxylation catalysts. By far, the preferred catalystsare compounds of V, W, Mo, Ti, Ta, Nb, Re, and Se.

The amount of metal in solution used as catalyst in the epoxidationprocess can be varied widely, although as a rule it is desirable to useat least 0.00001 mols and preferably 0.002 to 0.03 mols per mol ofhydroperoxide present. Amounts greater than about 0.1 mols seem tainingmolybdenum can be used as can salts thereof;

examples include phosphomolybdic acid and the sodium and potassium saltsthereof. Similar or analogous compounds of the other metals mentionedmay be used, as may mixtures thereof.

The catalytic components may be employed in the epoxidation reaction inthe form of a compound or mixture which is initially soluble in thereaction medium. While solubility will, to some extent depend on theparticular reaction medium employed, a suitably soluble substancecontemplated by the invention would include hydrocarbon soluble,organo-metallic compounds having a solubility in methanol at roomtemperature of at least 0.1 gram per liter. Illustrative soluble formsof the catalytic materials are the naphthenates, stearates, octoates,carbonyls and the like. Various chelates, association compounds and enolsalts, such, for examples, as aceto-acetonates may also be used.Specific and preferred catalytic compounds of this type for use in theinvention are the napthenates and carbonyls of molybdenum, vanadium andtungsten.

In the oxidation of the substrate, the ratio of substrate to organicperoxy compounds can vary over a wide range. Generally, mol ratios ofolefinic groups in the substrates to hydroperoxide broadly in the rangeof 0.5:1 to 100:1, desirably 1:1 to 20:1 and preferably 2:1 to 10:1 areemployed.

The concentration hydroperoxides in the substrate oxidation reactionmixture at the beginning of the reaction will normally be one percent ormore although lesser concentrations will be effective and can be used.

The substrate oxidation reaction can be carried out in the presence of asolvent, and in fact, it is generally desirable that one be used. Ingeneral, aqueous solvents are not contemplated. Among the suitablesubstances are hydrocarbons, which may be aliphatic, naphthenic oraromatic, and the oxygenated derivatives of these hydrocarbons.preferably, the solvent has the same carbon skeleton as thehydroperoxide used, so as to minimize or avoid solvent separationproblems.

Temperatures which can be employed in the epoxidation can vary quitewidely depending upon the reactivity and other characteristics of theparticular system. Temperatures broadly in the range of about 20 to200C., desirably to 150C., and preferably 50 to 120C. can be employed.The reaction is carried out at pressure conditions sufficient tomaintain a liquid phase. Although sub-atmospheric pressures can beemployed, pressures usually in the range of about atmospheric to about1,000 p.s.i.g. are most desirable.

In accordance with the present invention, the epoxidation effluent,which is of a catalytically acid nature insofar as alcohol dehydrationis concerned, is subjected to treatment in order to reduce the acidityto the extent that alcohol dehydration is avoided during subsequentwork-up.

In one, especially preferred embodiment, a basic material isincorporated with the effluent in an amount sufficient to overcome thecatalytic nature of said effluent. In this embodiment of the invention,the basic material can either be added before the actual epoxidationreaction or alternatively the basic material can be added aftercompletion of the reaction. Additionally, part can be added prior andpart subsequent to the epoxidation. Insofar as this embodiment of theinvention is concerned, reference is made to applicants copendingapplication Ser. No. 375,313, filed June 15, 1964 of which this is acontinuation in part now abandoned.

The basic substances which are employed in the present invention arealkali metal compounds or alkaline earth metal compounds. Particularlypreferred are the compounds of sodium, potassium, lithium, calcium,magnesium, rubidium, cesium, strontium and barium. Compounds which areemployed are those which most preferably are soluble in the reactionmedium. However, insoluble forms can be employedand are effective whendispersed in the reaction medium. Organic acid compounds such as a metalacetate, naphthenate, stearate, octoate, butyrate, which can be referredto as a group as naphthenates and alkanoates, and the like can beemployed. Additionally, inorganic salts such as Na carbonate, Mgcarbonate, trisodium phosphate, and the like can also be employed.Particularly preferred species of metal salts include sodiumnaphthenate, potassium stearate, magnesium carbonate, and the like.Hydroxides and oxides of alkali and alkali earth metal compounds can beused. Examples are NaOH, MgO, CaO, Ca(OH) K0 and the like. Alkoxides,e.g., Na ethylate, K cumylate, Na phenate, etc. can be used. Amides suchas NaNH can be used as can quaternary ammonium salts. In general, anycompound giving a basic reaction in water can be used.

The compound is employed in amounts of 0.05 to 10 mols/mol ofepoxidation catalyst, desirably 0.25 to 3.0 and preferably 0.50 to 1.50.

In an alternative embodiment of the invention, the epoxidation effluentis hydrogenated in order to reduce the acid catalyst characteristics.Most preferably, the product oxirane compound is first separated as bydistillation or extraction before this hydrogenation. However, it isquite possible to carry out the hydrogenation in the presence of theoxirane product.

Temperatures in the range 0 to 150C., preferably 20 to C. are employed.In this hydrogenation a suitable catalyst is employed: illustrativecatalysts are platinum, copper, nickel, zinc and the like knownhydrogenation catalysts. Pressures of 14.7 to 100 p.s.i.a. arepreferred. Hydrogenation times of the order of 2 minutes to 1 hour arepreferable.

In still another embodiment of the invention, the epoxidation effluentis reacted with a chemical reducing agent under conditions effective toreduce the acid catalyst characteristics thereof. Some typical reducingagents include sodium bisulfit'e, ferrous salts, compounds containingiodide ion, ascorbic acid an other reducing agents known to the artincluding hydroquinone.

Appropriate temperatures are 0 to 150C., preferably 30 to C. Although itis desirable to remove the product oxirane compound prior to thechemcial reduction, this is not necessary for successful practice of theinvention.

The following examples illustrate the invention:

EXAMPLE I To a pressure reaction is charged 20 grams of a 34.6 wt.percent solution of alpha phenyl ethyl hydroperoxide in ehtyl benzene,20 grams of propylene and 0.2 grams of molybdenum naphthenate solution(5 wt. percent M0). The mixture is reacted for 1 hour at l 10C.Hydroperoxide conversion essentially to alpha phenyl ethanol is 97.2percent and selectivity to propylene oxide based on hydroperoxide is70.8 percent.

The reaction mixture which is highly acidic in nature is distilled andpropylene and propylene oxide separated as overhead products from abottoms fraction.

The characteristics of the bottoms fraction are such that on beingheated to 146C., the alpha phenyl ethanol dehydrates to styrene whichinstantly polymerized and is lost to residue at a dehydration rate of244 percent per hour.

In accordance with the invention, the bottoms fraction is treated by theaddition of sodium in the form of sodium naphthenate in amount of 0.25mols Na per mol of M in the fraction.

As a result of this treatment, upon distillation at 147C. to separateethyl benzene and alpha phenyl ethanol, the alpha phenyl ethanoldehydration rate is only 3.2 percent per hour.

EXAMPLE II Example I is repeated except that 0.5 mols Na as sodiumnaphthenate is added per mol M0. The alpha phenyl ethanol dehydrationrate at 147C. is reduced to 1.2 percent per hour.

EXAMPLE III Example I is repeated through separation of propylene andpropylene oxide from the bottoms fraction.

The bottoms fraction is hydrogenated at 60C. and 100 p.s.i.g. withhydrogen over a nickel catalyst for 30 minutes. The rate of dehydrationof alpha phenyl ethanol at 150C of the treated fraction is 0.38 percentper hour.

EXAMPLE IV Example I is repeated through the separation of propylene andpropylene oxide from the bottoms fraction.

To the bottoms is added 0.1 mol sodium bisulfite per mol M0. The rate ofdehydration at 146C. of alpha phenyl ethanol in the treated fraction is9.5 percent per hour.

EXAMPLE V EXAMPLE VI Example is repeated except that the mixture ishydrogenated at 60C. and 100 p.s.i.g. with H over a nickel catalystafter the sodium naphthenate addition. Cumyl alcohol dehydration rate inthe resulting mixture is 0 at 150C. and at 170C.

EXAMPLE VII Example I is repeated using vanadium naphthenate inequivalent molar amount as epoxidation catalyst. Similar results areachieved.

EXAMPLE VIII Example I is repeated using tetrabutyl titanate inequivalent molar amount as epoxidation catalyst. Similar results areachieved.

EXAMPLE IX Example I is repeated using tungsten carbonyl in equivalentmolar amount as epoxidation catalyst. Similar results are achieved.

EXAMPLE X Example I is repeated using tantalum naphthenate in equivalentmolar amount as epoxidation catalyst. Similar results are achieved.

EXAMPLE XI Example I is repeated using niobium naphthenate in equivalentmolar amount as epoxidation catalyst. Similar results are achieved.

EXAMPLE XII Example I is repeated using rhenium heptoxide in equivalentmolar amount as epoxidation catalyst. Similar results are achieved.

EXAMPLE XIII Example I is repeated using selenium dioxide in equivalentmolar amounts as epoxidation catalyst. Similar results are achieved.

In accordance with the invention, the epoxidation effluent is treateduntil the acidic characteristics have been reduced to the extent thatthe dehydration rate of the alcohol formed by reduction of thehydroperoxide during the epoxidation is less than about 50 percent atC., preferably less than 10 percent at 140C. and desirably 0 to 5percent at 140C. I

The extent of a particular treatment is conveniently determined as byperiodic sampling and testing to determine the dehydration rate of thealcohol contained in the effluent.

What is claimed is:

l. The process for treating the product mixture from the epoxidation ofan olefinic hydrocarbon having two to 30 carbon atoms with an organichydroperoxide having the formula ROOH where is an alkyl, cycloalkyl oraralkyl radical having three to 20 carbon atoms at a temperature of 20to 200C. in the presence of a titanium, vanadium, chromium, selenium,zirconium, co-

lumbium, molybdenum, tellurium, tantalum, tungsten,

rhenium, or uranium catalyst in order to reduce the acidic catalystcharacteristics of said mixture at least to the extent that the rate ofdehydration of alcohol contained therein is less than 50 percent perhour at 140C. which comprises incorporating in saidmixture a basicmaterial selected from the group consisting of alkali metal and alkalineearth metal inorganic salts, hydroxides, oxides, alkoxides, amides,alkanoates, and napthenates in the amount of 0.05 to 10 mols per mol ofsaid catalyst and recovering said alcohol therefrom by distillation.

2. The process of claim 1 wherein the epoxidation catalyst is amolybdenum catalyst.

3. The process of claim 1 wherein the alkali metal and alkaline earthmetal inorganic salts used as the basic material incorporated arecarbonates or phosphates.

4. The process of claim 1 wherein the olefinic hydrocarbon is propylene.

5. The process for treating the product mixture from the epoxidation ofan olefinic hydrocarbon having two to 30 carbon atoms with an organichydroperoxide having the formula ROOH where R is an alkyl, cycloalkyl oraralkyl radical having three to 20 carbon atoms at a temperature of 20to 200C. in the presence of a titanium, vanadium, chromium, selenium,zirconium,- co-' lumbium, molybdenum, tellurium, tungsten, rhenium, oruranium catalyst in order to reduce the acidic catalyst characteristicsof said mixture at least to the extent that the rate of dehydration ofalcohol contained therein is less than 50 percent per hour at 140C.,said catalyst being used in the amount of 0.00001 to 0.1 mol per mol ofhydroperoxide, which comprises incorporating in said mixture a basicmaterial selected from the group consisting of alkali metal and alkalineearth metal inorganic salts, hydroxides, oxides, alkoxides, amides,alkanoates, and napthenates in the amount of 0.05 to 10 mols per mol ofsaid catalyst and recovering said alcohol therefrom by distillation.

6. The process of claim wherein the olefinic hydrocarbon is propylene.

7. The process for treating the product mixture from the epoxidation ofan olefinic hydrocarbon having two to 30 carbon atoms with an organichydroperoxide having the formula ROOH where R is an alkyl, cycloalkyl oraralkyl radical having three to 20 carbon atoms at a temperature of 20to 200C. in the presence of a titanium, vanadium, chromium, selenium,zirconium, columbium, molybdenum, tellurium, tantalum, tungsten,rhenium, or uranium catalyst in order to reduce the acidic catalystcharacteristics of said mixture at least to the extent that the rate ofdehydration of alcohol contained therein is less than 50 percent perhour at 140C., said catalyst being used in the amount of 0.0002 to 0.03mol per mol of hydroperoxide, which comprises incorporating in saidmixture a basic material selected from the group consisting of alkalimetal and alkaline earth metal inorganic salts, hydroxides, oxides,alkoxides, amides, alkanoates and napthenates in the amount of 0.05 tomols per mol of said catalyst and recovering said alcohol therefrom bydistillation.

' 8. The process f0 claim 7 wherein the olefinic hydrocarbon ispropylene.

9. The process for treating the product mixture from the epoxidation ofan olefinic hydrocarbon having two to 30 carbon atoms with an organichydroperoxide haing the formula ROOH where R is an alkyl, cycloalkyl oraralkyl radical having three to 20 carbon atoms at a temperature of -20to 200C. in the presence of a titanium, vanadium, chromium, selenium,zirconium,

columbium, molybdenum, tellurium, tantalum, tungsten, rhenium, oruranium catalyst in order to reduce the acidic catalyst characteristicsof said mixture at least to the extent that the rate of dehydration ofalcohol contained therein is less than 50 percent per hour at 140C.which comprises incorporating in said mixture a basic material selectedfrom the group consisting of alkali metal and alkaline earth metalinorganic salts, hydroxides, oxides, alkoxides, amides, alkanoates, andnapthenates in the amount of 0.25 to 3 mols per mol of said catalyst andrecovering said alcohol therefrom by distillation.

10. The process of claim 9 wherein the olefinic hydrocarbon ispropylene.

11. The process for treating the product mixture from the epoxidation ofpropylene with ethylbenzene hydroperoxide at a temperature of 20 to200C. in the presence of a titanium, vanadium, chromium, selenium,zirconium, columbium, molybdenum, tellurium, tantalum, tungsten, rheniumor uranium catalyst in order to reduce the acidic catalystcharacteristics of said mixture at least to the extent that the rate ofdehydration of alcohol contained therein is less than 50 percent perhour at 140C. which comprises incorporating in said mixture a basicmaterial selected from the group consisting of alkali metal and alkalineearth metal inorganic salts, hydroxides, oxides, alkoxides, amides,alkanoates, and napthenates in the amount of 0.05 to 10 mols per mol ofsaid catalyst and recovering alpha phenyl ethanol therefrom bydistillation.

12. The process for treating the product mixture from the epoxidation ofpropylene with cumene hydroperoxide at a temperature of 20 to 200C. inthe presence of a titanium, vanadium, chromium, selenium, zirconium,columbium, molybdenum, tellurium, tantalum, tungsten, rhenium or uraniumcatalyst in order to reduce the acidic catalyst characteristics of saidmixture at least to the extent that the rate of dehydration of alcoholcontained therein is less than 50 percohol therefrom by distillation.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Q PATENT NO.3,860,662

DATED Ianuary 14, 1975 INVENIORt'S) J K ll r It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 1, line 27, change "if to is Column 3, line 18, after"concentration" and before'hydroperoxides",

insert of Column 3, line 28, change "preferably" to Preferably C Column4, line 39, change "an" to and Column 4, line 52, change "ehtyl" toethyl Column 7, line 25, change "0.0002" to 0.002

9 Signed and Scaled this twenty-sixth D ay Of August 1975 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Anfflmg 1] Commissioner nflarents andTrademarks

1. THE PROCESS FOR TREATING THE PRODUCT MIXTURE FROM THE EPOXIDATION OFAN OLEFINIC HYDROCARBON HAVING TWO TO 30 CARBON ATOMS WITH AN ORGANICHYDROPEROXIDE HAVING THE FORMULA ROOH WHERE R IS AN ALKYL, CYCLOALKYL ORARALKYL RADICAL HAVING THREE TO 20 CARBON ATOMS AT A TEMPERATURE OF -20*TO 200*C. IN THE PRESENCE OF A TITANIUM, VANADIUM, CHROMIUM, SELENIUM,ZIRCONIUM, COLUMBIUM, MOLYBDENUM, TELLURIUM, TANTALUM, TUNGSTEN,RHENIUM, OR URANIUM CATALYST IN ORDER TO REDUCE THE ACIDIC CATALYSTCHARASTERISTICS OF SAID MIXTURE AT LEAST TO THE EXTENT THAT THE RATE OFDEHYDRATION OF ALCOHOL CONTAINED THEREIN IS LESS THAN 50 PERCENT PERHOUR AT 140*C. WHICH COMPRISES INCORPORATING IN SAID MIXTURE A BASICMATERIAL SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL AND ALKALINEEARTH METAL INORGANIC SALTS, HYDROXIDES, OXIDES, ALKOXIDES, AMIDES,ALKANOATES, AND NAPTHENATES IN THE AMOUNT OF 0.05 TO 10 MOLS PER MOL OFSAID CATALYST AND RECOVERING SAID ALCOHOL THEREFROM BY DISTILLATION. 2.The process of claim 1 wherein the epoxidation catalyst is a molybdenumcatalyst.
 3. The process of claim 1 wherein the alkali metal andalkaline earth metal inorganic salts used as the basic materialincorporated are carbonates or phosphates.
 4. The process of claim 1wherein the olefinic hydrocarbon is propylene.
 5. The process fortreating the product mixture from the epoxidation of an olefinichydrocarbon having two to 30 carbon atoms with an organic hydroperoxidehaving the formula ROOH where R is an alkyl, cycloalkyl or aralkylradical having three to 20 carbon atoms at a temperature of -20 to200*C. in the presence of a titanium, vanadium, chromium, selenium,zirconium, columbium, molybdenum, tellurium, tungsten, rhenium, oruranium catalyst in order to reduce the acidic catalyst characteristicsof said mixture at least to the extent that the rate of dehydration ofalcohol contained therein is less than 50 percent per hour at 140*C.,said catalyst being used in the amount of 0.00001 to 0.1 mol per mol ofhydroperoxide, which comprises incorporating in said mixture a basicmaterial selected from the group consisting of alkali metal and alkalineearth metal inorganic salts, hydroxides, oxides, alkoxides, amides,alkanoates, and napthenates in the amount of 0.05 to 10 mols per mol ofsaid catalyst and recovering said alcohol therefrom by distillation. 6.The process of claim 5 wherein the olefinic hydrocarbon is propylene. 7.The process for treating the product mixture from the epoxidation of anolefinic hydrocarbon having two to 30 carbon atoms with an organichydroperoxide having the formula ROOH where R is an alkyl, cycloalkyl oraralkyl radical having three to 20 carbon atoms at a temperature of -20to 200*C. in the presence of a titanium, vanadium, chromium, selenium,zirconium, columbium, molybdenum, tellurium, tantalum, tungsten,rhenium, or uranium catalyst in order to reduce the acidic catalystcharacteristics of said mixture at least to the extent that the rate ofdehydration of alcohol contained therein is less than 50 percent perhour at 140*C., said catalyst being used in the amount of 0.0002 to 0.03mol per mol of hydroperoxide, which comprises incorporating in saidmixture a basic material selected from the group consisting of alkalimetal and alkaline earth metal inorganic salts, hydroxides, oxides,alkoxides, amides, alkanoates and napthenates in the amount of 0.05 to10 mols per mol of said catalyst and recovering said alcohol therefromby distillation.
 8. The process fo claim 7 wherein the olefinichydrocarbon is propylene.
 9. The process for treating the productmixture from the epoxidation of an olefinic hydrocarbon having two to 30carbon atoms with an organic hydroperoxide haing the formula ROOH whereR is an alkyl, cycloalkyl or aralkyl radical having three to 20 carbonatoms at a temperature of -20 to 200*C. in the presence of a titanium,vanadium, chromium, selenium, zirconium, columbium, molybdenum,tellurium, tantalum, tungsten, rhenium, or uranium catalyst in order toreduce the acidic catalyst characteristics of said mixture at least tothe extent that the rate of dehydration of alcohol contained therein isless than 50 percent per hour at 140*C. which comprises incorporating insaid mixture a basic material selected from the group consisting ofalkali metal and alkaline earth metal inorganic salts, hydroxides,oxides, alkoxides, amides, alkanoates, and napthenates in the amount of0.25 to 3 mols per mol of said catalyst and recovering said alcoholtherefrom by distillation.
 10. The process of claim 9 wherein theolefinic hydrocarbon is propylene.
 11. The process for treating theproduct mixture from the epoxidation of propylene with ethylbenzenehydroperoxide at a teMperature of -20* to 200*C. in the presence of atitanium, vanadium, chromium, selenium, zirconium, columbium,molybdenum, tellurium, tantalum, tungsten, rhenium or uranium catalystin order to reduce the acidic catalyst characteristics of said mixtureat least to the extent that the rate of dehydration of alcohol containedtherein is less than 50 percent per hour at 140*C. which comprisesincorporating in said mixture a basic material selected from the groupconsisting of alkali metal and alkaline earth metal inorganic salts,hydroxides, oxides, alkoxides, amides, alkanoates, and napthenates inthe amount of 0.05 to 10 mols per mol of said catalyst and recoveringalpha phenyl ethanol therefrom by distillation.
 12. The process fortreating the product mixture from the epoxidation of propylene withcumene hydroperoxide at a temperature of -20* to 200*C. in the presenceof a titanium, vanadium, chromium, selenium, zirconium, columbium,molybdenum, tellurium, tantalum, tungsten, rhenium or uranium catalystin order to reduce the acidic catalyst characteristics of said mixtureat least to the extent that the rate of dehydration of alcohol containedtherein is less than 50 percent per hour at 140*C. which comprisesincorporating in said mixture a basic material selected from the groupconsisting of alkali metal and alkaline earth metal inorganic salts,hydroxides, oxides, alkoxides, amides, alkanoates, and napthenates inthe amount of 0.05 to 10 mols per mol of said catalyst and recoveringcumyl alcohol therefrom by distillation.